cis-Chlorido­bis­(4,4′-dimethyl-2,2′-bi­pyridine)­nitro­sylruthenium(II) bis­(hexa­fluoro­phosphate)

Mohammed, H.S.; Tassé, M.; Malfant, I.; Vendier, L.

doi:10.1107/S2414314617010136

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171013

https://doi.org/10.1107/S2414314617010136

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cis-Chloridobis(4,4′-dimethyl-2,2′-bipyridine)nitrosylruthenium(II) bis(hexafluorophosphate)

Hasan Shamran Mohammed,^a Marine Tassé,^a Isabelle Malfant ^a and Laure Vendier ^a ^*

^aLaboratoire de Chimie de Coordination, UPR-CNRS 8241, 205, route de Narbonne, 31077 Toulouse cedex, France
^*Correspondence e-mail: laure.vendier@lcc-toulouse.fr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 30 June 2017; accepted 7 July 2017; online 13 July 2017)

In the cation of the title complex, [RuCl(NO)(C₁₂H₁₂N₂)₂](PF₆)₂, the central Ru^II ion is sixfold coordinated by a chloride ion and a nitrosyl ligand, which are cis to one another, and by four N atoms of two 4,4′-dimethyl-2,2′-bipyridine ligands, in a slightly distorted octahedral geometry. One of the PF₆⁻ anions is located in a general position, while the other is composed of two half PF₆⁻ anions located on twofold rotation axes. The crystal packing is dominated by C—H⋯F hydrogen bonds, leading to the formation of a three-dimensional supramolecular structure. There are also C—H⋯Cl hydrogen bonds present.

Keywords: crystal structure; ruthenium(II); 4,4′-dimethyl-2,2′-bipyridine; chloride; nitrosyl; sixfold coordination; C—H⋯F hydrogen bonding.

CCDC reference: 1557221

Structure description

Ruthenium nitrosyl complexes have attracted significant attention over the last two decades, mainly due to their interesting photoreactivity properties. Ruthenium nitrosyl complexes can either induce photochromism (Schaniel et al., 2007b ) or NO photorelease (Rose & Mascharak, 2008 ). In the first case, photoisomerization along the ruthenium–nitrosyl bond (Ru—NO/Ru—ON) is observed in the solid state when the compounds are irradiated in the blue region (Schaniel et al., 2007a ; Cormary et al., 2009 , 2012 ). It offers technological applications as optical high-capacity storage devices (Imlau et al., 1999 ). In the latter case, irradiation at room temperature in the UV–visible region of solutions of ruthenium nitrosyl complexes gives rise to NO photorelease (Tfouni et al., 2003 ; Fry & Mascharak, 2011 ; Akl et al., 2014 ). This is very appealing because the nitric oxide has a significant role in various biological processes. It shows an ability to induce apoptosis and is involved in blood-pressure control, and also has antimicrobial activity (Hirst & Robson, 2007 ). Ruthenium nitrosyl complexes based on bipyridine ligands are of great interest because of their photoreactive properties (Togniolo et al., 2001 ). In the search for new systems, we have synthesized the title complex and report herein its crystal structure.

The cation of the title complex has a central Ru^II ion which is sixfold coordinated by a chloride ion and a nitrosyl ligand (Fig. 1), which are cis to one another, and by four N atoms of two 4,4′-dimethyl-2,2′-bipyridine ligands, in a slightly distorted octahedral geometry. One of the PF₆⁻ anions is located in a general position, while the other is composed of two half PF₆⁻ anions located on twofold rotation axes. The Ru1—N1—O1 angle is 178.6 (3)°, which is close to 180°, in agreement with the Enemark–Feltham notation for {RuNO}6 with Ru^II—NO⁺ and with the characteristic range of (NO) absorption around 1940 cm⁻¹ (Lahiri & Kaim, 2010 ).

Figure 1
The molecular structure of the [RuCl(NO)(dimethyl-2,2′-bipyridine)₂]²⁺ cation of the title complex, showing the atom labelling and 30% probability displacement ellipsoids.

The crystal packing is dominated by C—H⋯F hydrogen bonds, leading to the formation of a three-dimensional supramolecular structure (Table 1 and Fig. 2). There are also C—H⋯Cl hydrogen bonds present (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯F2ⁱ	0.95	2.54	3.328 (5)	141
C5—H5⋯F9ⁱⁱ	0.95	2.51	3.310 (5)	141
C8—H8⋯Cl1	0.95	2.75	3.353 (4)	122
C15—H15⋯Cl1ⁱⁱⁱ	0.95	2.80	3.660 (4)	152
C18—H18⋯F11^iv	0.95	2.49	3.215 (5)	133
C18—H18⋯F4^v	0.95	2.32	3.064 (5)	135
C19—H19⋯F13^vi	0.95	2.54	3.208 (5)	127
C21—H21⋯F8^vii	0.95	2.53	3.433 (5)	159
C22—H22⋯F1ⁱⁱ	0.95	2.32	3.253 (5)	166
C25—H25A⋯F4ⁱⁱ	0.98	2.50	3.358 (6)	147
C25—H25C⋯F9	0.98	2.39	3.228 (6)	143
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) x, y+1, z; (v) $[x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, y+1, -z+{\script{3\over 2}}]$ ; (vii) x, y-1, z.

Figure 2
A view along the b axis of the crystal packing of the title complex. The C—H⋯F hydrogen bonds are shown as dashed lines (see Table 1

) and only the H atoms involved in these interactions have been included.

Synthesis and crystallization

Synthesis of [RuCl₂(4,4′-dimethyl-2,2′-bipyridine)₂], (I)

DMF (15 ml) was bubbled with argon for 15 min. Lithium chloride (406 mg, 9.6 mmol) was dissolved in DMF (5 ml) with stirring for 15 min. Ruthenium chloride, (III) (250 mg, 1.2 mmol), was dissolved in DMF (5 ml). 4,4′-Dimethyl-2,2′-bipyridine (406 mg, 2.4 mmol) was dissolved in DMF (5 ml). The lithium chloride solution was added to the ruthenium chloride solution via cannula under argon. The 4,4′-dimethyl-2,2′-bipyridine solution was added to the above solution dropwise via cannula under argon. The reaction mixture was refluxed for 6 h at 413 K. The volume of the solution was decreased to half using a rotary evaporator. Acetone (50 ml) was added to the mixture and it was placed in an ice bath for 4 h. The dark-red precipitate that formed was filtered off, washed with distilled water and dried (yield 392 mg, 60.4%). Analysis calculated for C₂₄H₂₄Cl₂N₄Ru: C 53.34, H 4.48, N 10.37%; found: C 53.44, H 4.53, N 10.30%. IR (KBr) cm⁻¹: 3041 (C—H aromatic), 2910 (C—H aliphatic), 1615 (C=N), 1446 (C=C), 825 (C—H rock), 551 (C—H rock).

Synthesis of [Ru(NO₂)₂(4,4′-dimethyl-2,2′-bipyridine)₂], (II)

Compound (I) (305 mg, 0.56 mmol) was dissolved in distilled water (20 ml) and the red solution was refluxed for 30 min, then filtered. NaNO₂ (156.5 mg, 2.24 mmol) dissolved in distilled water (5 ml) and was added to the filtrate and the reaction mixture was refluxed for 1 h at 373 K. The mixture was placed in an ice bath for 1 h then filtered. The brown precipitate obtained was washed with distilled water and dried (yield 203 mg, 64.5%). Analysis calculated for C₂₄H₂₄N₆O₄Ru: C 51.33, H 4.31, N 14.97%; found: C 51.41, H 4.37, N 14.84%. ¹H NMR (300 MHz, DMSO-d₆, 298 K): δ 9.50 (2H1,1′, d, J = 5.85 Hz), 8.51 (2H3,3′, s), 8.41 (2H4,4′, s), 7.64 (2H2,2′, dd, J = 5.71, 1.18 Hz), 7.32 (2H6,6′, d, J = 5.74 Hz), 7.08 (2H5,5′, dd, J = 5.72, 1.00 Hz), 2.61 (6H, s, 2CH₃), 2.38 (6H, s, 2CH₃). IR (KBr) cm⁻¹: 3071 (C—H aromatic), 2920 (C—H aliphatic), 1616 (C=N), 1447 (C=C), 1320 (NO₂)_asy, 1272 (NO₂)_sy, 1039, 825, 551 due to (C—H) deformation.

Synthesis of [RuCl(NO)(dimethyl-2,2′-bipyridine)₂](PF₆)₂

Compound (II) (170 mg, 0.30 mmol) was dissolved in HCl (24 ml, 37%). The reaction mixture was refluxed for 1 h at 373 K and then left to cool to room temperature. NH₄PF₆ (195 mg, 1.2 mmol) dissolved in distilled water (2 ml) was added to the reaction mixture. The orange precipitate that formed was filtered off, washed with distilled water, then diethyl ether and dried (yield 154 mg, 62%). IR (KBr) cm⁻¹: 3088 (C—H aromatic), 2905 (C—H aliphatic), 1940 (N=O), 1618 (C=N), 1428(C=C), 835 (P—F).

Analysis calculated for C24H₂₄ClF₁₂N₅OP₂Ru: C 34.94, H 2.93, N 8.49%; found: C 34.84, H 2.85, N 8.40%. ¹H NMR (300 MHz, DMSO-d₆, 298 K): δ 9.23 (1H1, d, J = 5.99 Hz), 9.11 (1H1`, d, J = 5.92 Hz), 9.00 (1H3, d, 1.88), 8.92 (1H3`, d, J = 1.76 Hz), 8.86 (1H4, d, J = 1.86 Hz), 8.82 (1H4`, d, J = 1.82 Hz), 8.06 (1H2, d, J = 6.11 Hz), 8.00 (1H2`, d, J = 6.22 Hz), 7.82 (1H6, d, J = 5.94 Hz), 7.54 (1H5, dd, J = 6.10, 1.77 Hz), 7.43 (1H5`, J = 5.96, 1.80 Hz), 7.26 (1H6`, d, J = 6.02 Hz), 2.76 (3H, s, CH₃), 2.74 (3H, s, CH₃), 2.56 (3H, s, CH₃), 2.53 (3H, s, CH₃). UV–Vis in acetonitrile at 298 K, λ nm (∊ M⁻¹ cm⁻¹): 295 (24273), 323 (16554). Yellow plate-like crystals of the title complex were obtained by slow diffusion of diethyl ether into an acetone solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[RuCl(NO)(C₁₂H₁₂N₂)₂](PF₆)₂
M_r	824.94
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	173
a, b, c (Å)	18.6926 (12), 8.1573 (5), 20.3841 (13)
β (°)	102.828 (3)
V (Å³)	3030.6 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.82
Crystal size (mm)	0.15 × 0.08 × 0.02

Data collection
Diffractometer	Bruker Kappa APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.847, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	127079, 6196, 5805
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.108, 1.32
No. of reflections	6196
No. of parameters	421
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.19, −0.73
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick 2008 ), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ) and WinGX (Farrugia, 2012).

Structural data

CCDC reference: 1557221

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617010136/su4156sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010136/su4156Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

cis-Chloridobis(4,4'-dimethyl-2,2'-bipyridine)nitrosylruthenium(II) bis(hexafluorophosphate) top

Crystal data top

[RuCl(NO)(C₁₂H₁₂N₂)₂](PF₆)₂	F(000) = 1640
M_r = 824.94	D_x = 1.808 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 9501 reflections
a = 18.6926 (12) Å	θ = 2.7–29.2°
b = 8.1573 (5) Å	µ = 0.82 mm⁻¹
c = 20.3841 (13) Å	T = 173 K
β = 102.828 (3)°	Plate, yellow
V = 3030.6 (3) Å³	0.15 × 0.08 × 0.02 mm
Z = 4

Data collection top

Bruker Kappa APEXII diffractometer	6196 independent reflections
Radiation source: microsource	5805 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω–φ scans	θ_max = 26.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −23→23
T_min = 0.847, T_max = 0.989	k = −10→10
127079 measured reflections	l = −25→25

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.32	w = 1/[σ²(F_o²) + (0.0177P)² + 13.0961P] where P = (F_o² + 2F_c²)/3
6196 reflections	(Δ/σ)_max < 0.001
421 parameters	Δρ_max = 1.19 e Å⁻³
0 restraints	Δρ_min = −0.73 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ru1	0.295920 (17)	0.32238 (4)	0.480073 (15)	0.01836 (9)
F12	0.22407 (15)	−0.3588 (3)	0.66961 (12)	0.0334 (6)
Cl1	0.39303 (6)	0.13222 (13)	0.51121 (6)	0.0283 (2)
P2	0.25	0.8827 (2)	0.25	0.0294 (4)
P1	0.03457 (6)	0.28288 (15)	0.36131 (6)	0.0278 (3)
F8	0.25	1.0779 (5)	0.25	0.0410 (10)
F7	0.25	0.6866 (7)	0.25	0.094 (2)
F4	−0.00952 (17)	0.3316 (4)	0.28780 (14)	0.0471 (8)
F2	−0.03599 (15)	0.1995 (4)	0.37854 (14)	0.0390 (7)
F6	0.01399 (17)	0.4528 (4)	0.39047 (17)	0.0491 (8)
F1	0.10714 (15)	0.3653 (4)	0.34570 (13)	0.0402 (7)
F3	0.08241 (15)	0.2338 (4)	0.43490 (12)	0.0373 (7)
F5	0.05578 (15)	0.1119 (4)	0.33278 (14)	0.0375 (6)
F10	0.29501 (17)	0.8830 (5)	0.32644 (14)	0.0504 (8)
F9	0.32424 (18)	0.8816 (5)	0.22524 (15)	0.0562 (10)
N1	0.21674 (17)	0.5015 (4)	0.46897 (16)	0.0175 (7)
N2	0.24267 (18)	0.2538 (4)	0.55481 (16)	0.0197 (7)
N3	0.35224 (18)	0.4258 (4)	0.41381 (16)	0.0210 (7)
F11	0.30891 (14)	−0.2203 (3)	0.74521 (13)	0.0292 (6)
C1	0.1747 (2)	0.4963 (5)	0.51577 (18)	0.0177 (8)
C2	0.1216 (2)	0.6127 (5)	0.5158 (2)	0.0232 (8)
H2	0.0939	0.6094	0.5496	0.028*
C3	0.1077 (3)	0.7348 (6)	0.4675 (2)	0.0294 (10)
C4	0.0469 (3)	0.8564 (6)	0.4652 (3)	0.0465 (14)
H4A	0.0058	0.8029	0.4792	0.07*
H4B	0.0304	0.898	0.4192	0.07*
H4C	0.0648	0.9478	0.4956	0.07*
C5	0.1509 (2)	0.7352 (5)	0.4195 (2)	0.0257 (9)
H5	0.1428	0.8156	0.3849	0.031*
C6	0.2047 (2)	0.6205 (5)	0.42230 (19)	0.0227 (8)
H6	0.2346	0.625	0.3902	0.027*
C7	0.1877 (2)	0.3556 (5)	0.56216 (18)	0.0175 (8)
C8	0.2559 (2)	0.1187 (5)	0.5928 (2)	0.0264 (9)
H8	0.2944	0.0477	0.5873	0.032*
C9	0.2157 (2)	0.0788 (5)	0.6395 (2)	0.0283 (9)
H9	0.2259	−0.0193	0.665	0.034*
C10	0.1600 (2)	0.1834 (5)	0.6493 (2)	0.0237 (9)
C11	0.1467 (2)	0.3241 (5)	0.60945 (19)	0.0205 (8)
H11	0.1093	0.3984	0.6148	0.025*
C12	0.1158 (3)	0.1481 (6)	0.7011 (2)	0.0304 (10)
H12A	0.0719	0.2173	0.6926	0.046*
H12B	0.1456	0.1715	0.7461	0.046*
H12C	0.1013	0.0324	0.6984	0.046*
N4	0.36093 (17)	0.4951 (4)	0.54082 (16)	0.0193 (7)
C14	0.4023 (2)	0.5919 (5)	0.50946 (19)	0.0174 (8)
C15	0.4448 (2)	0.7176 (5)	0.5430 (2)	0.0216 (8)
H15	0.4735	0.7832	0.5201	0.026*
C16	0.4458 (2)	0.7483 (5)	0.6106 (2)	0.0224 (8)
C17	0.4901 (3)	0.8868 (6)	0.6478 (2)	0.0315 (10)
H17A	0.4575	0.9785	0.6519	0.047*
H17B	0.5266	0.9228	0.623	0.047*
H17C	0.5151	0.8496	0.6928	0.047*
C18	0.4032 (2)	0.6491 (5)	0.6418 (2)	0.0238 (9)
H18	0.4024	0.6663	0.6877	0.029*
C19	0.3620 (2)	0.5251 (5)	0.60590 (19)	0.0224 (8)
H19	0.3332	0.458	0.6281	0.027*
C20	0.3978 (2)	0.5509 (5)	0.43805 (19)	0.0193 (8)
C21	0.3468 (2)	0.3789 (6)	0.3495 (2)	0.0281 (10)
H21	0.3156	0.2896	0.3323	0.034*
C22	0.3850 (2)	0.4564 (6)	0.3079 (2)	0.0301 (10)
H22	0.3796	0.42	0.2628	0.036*
C23	0.4310 (2)	0.5868 (6)	0.3311 (2)	0.0262 (9)
C24	0.4372 (2)	0.6333 (5)	0.3981 (2)	0.0192 (8)
H24	0.4684	0.7217	0.4163	0.023*
C25	0.4720 (3)	0.6781 (6)	0.2869 (2)	0.0346 (11)
H25A	0.477	0.6081	0.2491	0.052*
H25B	0.5208	0.7081	0.3131	0.052*
H25C	0.4448	0.7776	0.2697	0.052*
N5	0.24250 (18)	0.1847 (5)	0.42268 (17)	0.0234 (7)
O1	0.20981 (18)	0.0961 (5)	0.38590 (18)	0.0408 (9)
P3	0.25	−0.35977 (18)	0.75	0.0220 (3)
F13	0.19066 (17)	−0.4991 (3)	0.75495 (14)	0.0386 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01756 (16)	0.02110 (17)	0.01676 (15)	−0.00024 (13)	0.00453 (11)	−0.00084 (13)
F12	0.0493 (16)	0.0329 (15)	0.0176 (12)	−0.0077 (12)	0.0071 (11)	−0.0033 (11)
Cl1	0.0214 (5)	0.0274 (5)	0.0362 (6)	0.0041 (4)	0.0063 (4)	0.0019 (4)
P2	0.0402 (9)	0.0288 (9)	0.0226 (8)	0	0.0140 (7)	0
P1	0.0281 (6)	0.0351 (7)	0.0197 (5)	−0.0093 (5)	0.0043 (4)	−0.0013 (5)
F8	0.047 (2)	0.029 (2)	0.044 (2)	0	0.0035 (19)	0
F7	0.159 (7)	0.030 (3)	0.094 (5)	0	0.030 (4)	0
F4	0.0472 (17)	0.054 (2)	0.0311 (15)	−0.0047 (15)	−0.0106 (13)	0.0051 (14)
F2	0.0322 (14)	0.0447 (17)	0.0429 (16)	−0.0089 (13)	0.0139 (12)	−0.0072 (14)
F6	0.0451 (17)	0.0423 (18)	0.060 (2)	−0.0054 (15)	0.0108 (15)	−0.0110 (16)
F1	0.0362 (15)	0.0566 (19)	0.0266 (13)	−0.0175 (14)	0.0047 (11)	0.0056 (13)
F3	0.0426 (16)	0.0464 (17)	0.0205 (13)	−0.0140 (13)	0.0021 (11)	0.0029 (12)
F5	0.0359 (15)	0.0420 (16)	0.0345 (15)	−0.0084 (13)	0.0076 (12)	−0.0046 (13)
F10	0.0526 (19)	0.076 (2)	0.0237 (14)	0.0191 (17)	0.0101 (13)	0.0109 (15)
F9	0.0478 (18)	0.090 (3)	0.0360 (16)	0.0260 (18)	0.0211 (14)	0.0060 (17)
N1	0.0207 (16)	0.0155 (16)	0.0168 (15)	−0.0032 (13)	0.0049 (13)	−0.0017 (13)
N2	0.0193 (16)	0.0222 (17)	0.0179 (16)	0.0005 (14)	0.0050 (13)	0.0031 (14)
N3	0.0197 (16)	0.0265 (19)	0.0179 (16)	−0.0011 (14)	0.0063 (13)	−0.0027 (14)
F11	0.0336 (14)	0.0253 (13)	0.0307 (13)	−0.0043 (11)	0.0115 (11)	−0.0003 (11)
C1	0.0210 (18)	0.0181 (19)	0.0131 (17)	−0.0046 (15)	0.0020 (14)	−0.0005 (15)
C2	0.027 (2)	0.022 (2)	0.022 (2)	0.0036 (17)	0.0086 (16)	0.0009 (16)
C3	0.034 (2)	0.027 (2)	0.028 (2)	0.0041 (19)	0.0089 (19)	0.0046 (18)
C4	0.063 (4)	0.031 (3)	0.051 (3)	0.025 (3)	0.024 (3)	0.017 (2)
C5	0.032 (2)	0.022 (2)	0.022 (2)	0.0008 (18)	0.0042 (17)	0.0041 (17)
C6	0.030 (2)	0.024 (2)	0.0153 (18)	−0.0055 (17)	0.0072 (16)	0.0050 (16)
C7	0.0203 (18)	0.0155 (19)	0.0151 (17)	−0.0018 (15)	0.0008 (14)	−0.0016 (14)
C8	0.026 (2)	0.023 (2)	0.030 (2)	0.0057 (17)	0.0066 (18)	0.0071 (18)
C9	0.034 (2)	0.021 (2)	0.029 (2)	0.0014 (18)	0.0058 (18)	0.0093 (18)
C10	0.029 (2)	0.024 (2)	0.0184 (19)	−0.0072 (18)	0.0054 (16)	0.0012 (17)
C11	0.0236 (19)	0.0180 (19)	0.0200 (19)	0.0002 (16)	0.0052 (15)	−0.0023 (16)
C12	0.040 (3)	0.028 (2)	0.027 (2)	−0.002 (2)	0.0149 (19)	0.0069 (18)
N4	0.0185 (16)	0.0229 (17)	0.0160 (15)	0.0018 (14)	0.0025 (13)	0.0005 (13)
C14	0.0161 (18)	0.0183 (19)	0.0181 (18)	0.0048 (15)	0.0043 (14)	0.0005 (15)
C15	0.0215 (19)	0.022 (2)	0.022 (2)	0.0022 (16)	0.0065 (16)	0.0000 (16)
C16	0.022 (2)	0.021 (2)	0.022 (2)	0.0030 (17)	−0.0006 (16)	−0.0015 (16)
C17	0.037 (3)	0.028 (2)	0.027 (2)	−0.002 (2)	0.0007 (19)	−0.0045 (19)
C18	0.024 (2)	0.031 (2)	0.0157 (18)	0.0029 (18)	0.0038 (15)	−0.0011 (17)
C19	0.022 (2)	0.029 (2)	0.0169 (18)	−0.0008 (17)	0.0048 (15)	0.0014 (17)
C20	0.0195 (19)	0.0193 (19)	0.0200 (19)	0.0061 (16)	0.0062 (15)	0.0006 (16)
C21	0.029 (2)	0.037 (3)	0.019 (2)	−0.0050 (19)	0.0058 (17)	−0.0088 (18)
C22	0.033 (2)	0.040 (3)	0.019 (2)	0.002 (2)	0.0089 (18)	−0.0045 (19)
C23	0.025 (2)	0.032 (2)	0.023 (2)	0.0056 (18)	0.0102 (17)	0.0041 (18)
C24	0.0215 (19)	0.0122 (18)	0.024 (2)	0.0010 (15)	0.0065 (16)	0.0010 (15)
C25	0.040 (3)	0.040 (3)	0.027 (2)	−0.001 (2)	0.017 (2)	0.003 (2)
N5	0.0200 (16)	0.0264 (19)	0.0266 (18)	0.0014 (15)	0.0111 (14)	−0.0050 (16)
O1	0.0331 (18)	0.045 (2)	0.047 (2)	−0.0143 (16)	0.0149 (16)	−0.0238 (18)
P3	0.0354 (8)	0.0145 (7)	0.0174 (7)	0	0.0087 (6)	0
F13	0.0607 (19)	0.0245 (14)	0.0369 (15)	−0.0149 (13)	0.0240 (14)	−0.0079 (12)

Geometric parameters (Å, º) top

Ru1—N5	1.763 (4)	C8—H8	0.95
Ru1—N1	2.056 (3)	C9—C10	1.394 (6)
Ru1—N3	2.068 (3)	C9—H9	0.95
Ru1—N2	2.073 (3)	C10—C11	1.395 (6)
Ru1—N4	2.080 (3)	C10—C12	1.506 (6)
Ru1—Cl1	2.3648 (11)	C11—H11	0.95
F12—P3	1.602 (2)	C12—H12A	0.98
P2—F9	1.578 (3)	C12—H12B	0.98
P2—F9ⁱ	1.578 (3)	C12—H12C	0.98
P2—F8	1.593 (4)	N4—C19	1.345 (5)
P2—F10ⁱ	1.598 (3)	N4—C14	1.360 (5)
P2—F10	1.598 (3)	C14—C15	1.382 (6)
P2—F7	1.599 (6)	C14—C20	1.478 (5)
P1—F6	1.589 (3)	C15—C16	1.397 (6)
P1—F2	1.591 (3)	C15—H15	0.95
P1—F4	1.592 (3)	C16—C18	1.384 (6)
P1—F5	1.595 (3)	C16—C17	1.503 (6)
P1—F1	1.608 (3)	C17—H17A	0.98
P1—F3	1.617 (3)	C17—H17B	0.98
N1—C6	1.343 (5)	C17—H17C	0.98
N1—C1	1.365 (5)	C18—C19	1.379 (6)
N2—C8	1.337 (5)	C18—H18	0.95
N2—C7	1.355 (5)	C19—H19	0.95
N3—C21	1.348 (5)	C20—C24	1.387 (5)
N3—C20	1.350 (5)	C21—C22	1.377 (6)
F11—P3	1.601 (3)	C21—H21	0.95
C1—C2	1.373 (6)	C22—C23	1.384 (7)
C1—C7	1.473 (5)	C22—H22	0.95
C2—C3	1.384 (6)	C23—C24	1.397 (6)
C2—H2	0.95	C23—C25	1.502 (6)
C3—C5	1.400 (6)	C24—H24	0.95
C3—C4	1.502 (6)	C25—H25A	0.98
C4—H4A	0.98	C25—H25B	0.98
C4—H4B	0.98	C25—H25C	0.98
C4—H4C	0.98	N5—O1	1.120 (5)
C5—C6	1.365 (6)	P3—F11ⁱⁱ	1.601 (3)
C5—H5	0.95	P3—F12ⁱⁱ	1.602 (2)
C6—H6	0.95	P3—F13	1.607 (3)
C7—C11	1.383 (5)	P3—F13ⁱⁱ	1.607 (3)
C8—C9	1.377 (6)

N5—Ru1—N1	95.26 (14)	N2—C8—H8	118.8
N5—Ru1—N3	97.01 (14)	C9—C8—H8	118.8
N1—Ru1—N3	95.54 (13)	C8—C9—C10	119.5 (4)
N5—Ru1—N2	91.27 (15)	C8—C9—H9	120.2
N1—Ru1—N2	79.70 (13)	C10—C9—H9	120.2
N3—Ru1—N2	170.83 (14)	C9—C10—C11	117.6 (4)
N5—Ru1—N4	175.15 (15)	C9—C10—C12	121.7 (4)
N1—Ru1—N4	84.00 (13)	C11—C10—C12	120.7 (4)
N3—Ru1—N4	78.32 (13)	C7—C11—C10	120.2 (4)
N2—Ru1—N4	93.30 (13)	C7—C11—H11	119.9
N5—Ru1—Cl1	92.77 (12)	C10—C11—H11	119.9
N1—Ru1—Cl1	170.58 (9)	C10—C12—H12A	109.5
N3—Ru1—Cl1	88.35 (10)	C10—C12—H12B	109.5
N2—Ru1—Cl1	95.22 (10)	H12A—C12—H12B	109.5
N4—Ru1—Cl1	88.42 (9)	C10—C12—H12C	109.5
F9—P2—F9ⁱ	179.4 (3)	H12A—C12—H12C	109.5
F9—P2—F8	90.31 (16)	H12B—C12—H12C	109.5
F9ⁱ—P2—F8	90.31 (16)	C19—N4—C14	118.2 (3)
F9—P2—F10ⁱ	89.89 (16)	C19—N4—Ru1	126.1 (3)
F9ⁱ—P2—F10ⁱ	90.11 (16)	C14—N4—Ru1	115.5 (2)
F8—P2—F10ⁱ	89.90 (15)	N4—C14—C15	121.5 (4)
F9—P2—F10	90.11 (16)	N4—C14—C20	114.7 (3)
F9ⁱ—P2—F10	89.89 (16)	C15—C14—C20	123.7 (4)
F8—P2—F10	89.90 (15)	C14—C15—C16	120.1 (4)
F10ⁱ—P2—F10	179.8 (3)	C14—C15—H15	120
F9—P2—F7	89.69 (16)	C16—C15—H15	120
F9ⁱ—P2—F7	89.69 (16)	C18—C16—C15	117.7 (4)
F8—P2—F7	180.000 (2)	C18—C16—C17	121.1 (4)
F10ⁱ—P2—F7	90.10 (15)	C15—C16—C17	121.2 (4)
F10—P2—F7	90.10 (15)	C16—C17—H17A	109.5
F6—P1—F2	90.51 (17)	C16—C17—H17B	109.5
F6—P1—F4	90.95 (19)	H17A—C17—H17B	109.5
F2—P1—F4	91.90 (17)	C16—C17—H17C	109.5
F6—P1—F5	179.40 (19)	H17A—C17—H17C	109.5
F2—P1—F5	89.54 (16)	H17B—C17—H17C	109.5
F4—P1—F5	89.65 (17)	C19—C18—C16	119.8 (4)
F6—P1—F1	89.67 (18)	C19—C18—H18	120.1
F2—P1—F1	178.51 (17)	C16—C18—H18	120.1
F4—P1—F1	89.57 (16)	N4—C19—C18	122.8 (4)
F5—P1—F1	90.26 (16)	N4—C19—H19	118.6
F6—P1—F3	89.92 (17)	C18—C19—H19	118.6
F2—P1—F3	90.25 (15)	N3—C20—C24	121.7 (4)
F4—P1—F3	177.67 (17)	N3—C20—C14	115.1 (3)
F5—P1—F3	89.47 (16)	C24—C20—C14	123.2 (4)
F1—P1—F3	88.28 (15)	N3—C21—C22	122.1 (4)
C6—N1—C1	119.0 (3)	N3—C21—H21	119
C6—N1—Ru1	126.5 (3)	C22—C21—H21	119
C1—N1—Ru1	114.4 (3)	C21—C22—C23	120.7 (4)
C8—N2—C7	119.2 (3)	C21—C22—H22	119.6
C8—N2—Ru1	126.2 (3)	C23—C22—H22	119.6
C7—N2—Ru1	114.5 (3)	C22—C23—C24	116.9 (4)
C21—N3—C20	118.4 (4)	C22—C23—C25	122.5 (4)
C21—N3—Ru1	125.5 (3)	C24—C23—C25	120.6 (4)
C20—N3—Ru1	116.1 (3)	C20—C24—C23	120.3 (4)
N1—C1—C2	120.5 (4)	C20—C24—H24	119.9
N1—C1—C7	115.7 (3)	C23—C24—H24	119.9
C2—C1—C7	123.8 (4)	C23—C25—H25A	109.5
C1—C2—C3	121.3 (4)	C23—C25—H25B	109.5
C1—C2—H2	119.4	H25A—C25—H25B	109.5
C3—C2—H2	119.4	C23—C25—H25C	109.5
C2—C3—C5	116.9 (4)	H25A—C25—H25C	109.5
C2—C3—C4	121.3 (4)	H25B—C25—H25C	109.5
C5—C3—C4	121.8 (4)	O1—N5—Ru1	178.6 (3)
C3—C4—H4A	109.5	F11—P3—F11ⁱⁱ	89.5 (2)
C3—C4—H4B	109.5	F11—P3—F12	89.43 (14)
H4A—C4—H4B	109.5	F11ⁱⁱ—P3—F12	90.16 (14)
C3—C4—H4C	109.5	F11—P3—F12ⁱⁱ	90.16 (14)
H4A—C4—H4C	109.5	F11ⁱⁱ—P3—F12ⁱⁱ	89.43 (14)
H4B—C4—H4C	109.5	F12—P3—F12ⁱⁱ	179.4 (2)
C6—C5—C3	120.2 (4)	F11—P3—F13	179.73 (16)
C6—C5—H5	119.9	F11ⁱⁱ—P3—F13	90.28 (14)
C3—C5—H5	119.9	F12—P3—F13	90.66 (14)
N1—C6—C5	122.1 (4)	F12ⁱⁱ—P3—F13	89.75 (15)
N1—C6—H6	119	F11—P3—F13ⁱⁱ	90.28 (14)
C5—C6—H6	119	F11ⁱⁱ—P3—F13ⁱⁱ	179.73 (17)
N2—C7—C11	121.0 (4)	F12—P3—F13ⁱⁱ	89.75 (15)
N2—C7—C1	115.4 (3)	F12ⁱⁱ—P3—F13ⁱⁱ	90.66 (14)
C11—C7—C1	123.6 (4)	F13—P3—F13ⁱⁱ	90.0 (2)
N2—C8—C9	122.4 (4)

Symmetry codes: (i) −x+1/2, y, −z+1/2; (ii) −x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F2ⁱⁱⁱ	0.95	2.54	3.328 (5)	141
C5—H5···F9ⁱ	0.95	2.51	3.310 (5)	141
C8—H8···Cl1	0.95	2.75	3.353 (4)	122
C15—H15···Cl1^iv	0.95	2.80	3.660 (4)	152
C18—H18···F11^v	0.95	2.49	3.215 (5)	133
C18—H18···F4^vi	0.95	2.32	3.064 (5)	135
C19—H19···F13^vii	0.95	2.54	3.208 (5)	127
C21—H21···F8^viii	0.95	2.53	3.433 (5)	159
C22—H22···F1ⁱ	0.95	2.32	3.253 (5)	166
C25—H25A···F4ⁱ	0.98	2.50	3.358 (6)	147
C25—H25C···F9	0.98	2.39	3.228 (6)	143

Symmetry codes: (i) −x+1/2, y, −z+1/2; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) x, y+1, z; (vi) x+1/2, −y+1, z+1/2; (vii) −x+1/2, y+1, −z+3/2; (viii) x, y−1, z.

Funding information

Funding for this research was provided by: Iraqi/French institution (grant to HSM); Campus France (award No. 776290J (Moyen-Orient) to HSM).

References

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